US4031130A - Aliphatic β-keto esters - Google Patents

Aliphatic β-keto esters Download PDF

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Publication number
US4031130A
US4031130A US05/557,268 US55726875A US4031130A US 4031130 A US4031130 A US 4031130A US 55726875 A US55726875 A US 55726875A US 4031130 A US4031130 A US 4031130A
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Prior art keywords
ketone
sodium
reaction
condensation agent
dialkyl
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US05/557,268
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English (en)
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Gunter Renner
Immo Boie
Quirin Scheben
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety

Definitions

  • This invention relates to a process for the production of aliphatic ⁇ -keto esters, more especially sterically hindered aliphatic ⁇ -keto esters, in excellent yields.
  • the synthesis of ⁇ -keto esters is known and is described, for example as Claisen's condensation, in numerous text books and publications.
  • carboxylic acid esters are reacted as the carbonyl component with C-H-acid carboxylic acid esters to form ⁇ -keto carboxylic acid esters in an inert solvent in the presence of at least equimolar quantities of basic catalysts such as, for example sodium hydride, sodium amide, triphenyl methyl sodium and alkali metal alcoholates, as condensation agents.
  • Basic catalysts such as, for example sodium hydride, sodium amide, triphenyl methyl sodium and alkali metal alcoholates, as condensation agents.
  • Mixed ester condensations are generally only carried out with formic acid esters as the carbonyl component because it is only in this way that
  • the pivalic acid chloride required for the reaction is difficult to process on account of its pungency, and the temperature at which the reaction is carried out is difficult to control, even in cases where freshly prepared magnesium alcoholate is used.
  • alkaline dissociation of the ⁇ -diketo carboxylic acid ester formed as intermediate results in the formation not only of pivaloyl acetic ester but also, through a secondary reaction, in the formation of aceto-acetic ester and pivalic acid. Accordingly, the pivaloyl acetic ester thus formed can only be obtained with difficulty in pure form from the mixture of ⁇ -keto esters by distillation.
  • aliphatic ⁇ -keto esters more especially sterically hindered aliphatic ⁇ -keto esters, can be obtained in improved yields by reacting dialkyl ketones with dialkyl carbonates and at least equimolar quantities of a basic condensation agent in known manner, using hexamethyl phosphoric acid triamide as solvent.
  • the invention relates to a process for the production of aliphatic ⁇ -keto esters, in which dialkyl ketones are introduced slowly into a solution of, preferably, excess dialkyl carbonate and at least an equivalent quantity of a basic condensation agent based on the dialkyl ketone, in hexamethyl phosphoric acid triamide at reaction temperatures in the range of from 20° to 80° C, and the reaction product formed subsequently coverted by acidification into the ⁇ -keto ester.
  • Basic condensation agents suitable for use according to the invention include alkali or alkaline earth metal alcoholates such as sodium methylate, sodium ethylate, potassium ethylate, potassium-t-butylate or magnesium ethylate, sodium amide, sodium hydride and triphenyl methyl sodium. Of the alcoholates, potassium-t-butylate is preferred.
  • the quantity in which the basic condensation agent is used should be at least equivalent to the quantity in which the dialkyl ketone is used. In cases where the alcoholates are used as condensation agents, it is preferred to use an excess of approximately 5%, although this may even be higher, especially in the case of potassium-t-butylate. In cases where sodium hydride is used as the condensation agent, it is preferred to use more than 2 mols of sodium hydride per mol of dialkyl ketone used.
  • Dialkyl carbonates suitable for use in accordance with the invention are compounds corresponding to the following general formula: ##STR1## in which the radicals R and R' may be the same or different and represent alkyl radicals preferably with 1 to 4 carbon atoms, such as propyl, isopropyl, methyl and, in particular, ethyl.
  • the preferred dialkyl carbonate is diethyl carbonate.
  • the quantity in which the dialkyl carbonate is used should be at least equivalent to the quantity in which the dialkyl ketone is used. However, the dialkyl carbonate is preferably used in a 2- to 10-molar excess.
  • the hexamethyl phosphoric acid triamide used as solvent should be employed in such a quantity that it accelerates the reaction to a sufficient extent. It is preferred to use at least 0.1 mol of hexamethyl phosphoric acid triamide per mol of dialkyl ketone to be reacted as solvent.
  • the hexamethyl phosphoric acid triamide may of course be used in larger quantities. If desired, the excess hexamethyl phosphoric acid triamide can be recovered from the aqueous phase by extraction with chloroform after the reaction mixture has been treated in the usual way on completion of the reaction, and reused.
  • the process according to the invention is suitable for the reaction of standard, known alkyl ketones and is particularly suitable for the reaction of ketones of the kind which can only be reacted with dialkyl carbonates with difficulty or in poor yields by conventional methods.
  • methyl alkyl ketones or methyl alkyl ketones which are monosubstituted, especially monoalkylated, on the methyl group are suitable for use as the dialkyl ketones which may be reacted in accordance with the invention to form ⁇ -keto esters, and can be reacted in high yields.
  • monoalkylated methyl alkyl ketones also include ketones of the kind whose alkyl substituents together form of multimembered aliphatic ring.
  • dialkyl ketones suitable for use in accordance with the invention are compounds corresponding to the following general formula: ##STR2## in which
  • R 1 represents an alkyl radical preferably with 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, dodecyl, octadecyl, more especially isopropyl or t-butyl, and
  • R 2 represents hydrogen or an alkyl group with 1 to 4 carbon atoms, more especially methyl or ethyl, in addition to which
  • R 1 and R 2 may together represent the atoms required to complete a multi-membered aliphatic ring, more especially 5- to 7-membered aliphatic ring, such as a cyclopentanone, cyclohexanone or cycloheptanone ring.
  • dialkyl ketones which can be reacted in accordance with the invention to form high yields of ⁇ -keto esters, are pinacolone, diethyl ketone, methyl isopropyl detone and cyclohexanone.
  • the process according to the invention is particularly suitable for the production of pivaloyl acetic esters which are acquiring increasing significance in practice for the preparation of pivaloyl yellow couplers for photographic purposes. It is of advantage in the process according to the invention to avoid an excess of dialkyl ketone in the reaction mixture consisting of the hexamethyl phosphoric acid triamide, the dialkyl carbonate and the basic condensation agent. This can with advantage be achieved by adding the ketone slowly and uniformly to the reaction mixture, so that there is only ever a small quantity of unreacted ketone present in the reaction mixture.
  • the solvent, hexamethyl phosphoric acid triamide can with advantage be diluted by the addition of another inert organic solvent.
  • the preferred, additional solvent is the dialkyl carbonate used for the reaction.
  • Benzene, toluene and xylene are also suitable.
  • the dialkyl ketone can be added to the reaction mixture either directly or in solution in an inert solvent.
  • alcoholates are used as the condensation agent, it is of advantage of the particular alcohol formed in the reaction mixture to be removed during the reaction by simultaneous distillation, and for its concentration to be kept as low as possible. Ideally, the alcohol should actually be removed from the reaction mixture at the moment it is formed.
  • the reaction is carried out by using the alcoholates corresponding to the dialkyl carbonate.
  • the reaction temperature is in the range from 20° to 80° C, and the fractions of alcohol formed during the reaction are distilled off through a column, optionally under a light vacuum of 100 to 500 Torr. Where it is used for example in molar quantities, the ketone is continuously added over a period of preferably more than 2 hours.
  • continuous addition apart from continuous addition in its strict sense, is also meant to include addition in small quantities and at brief time intervals as obtained, for example, by dropwise addition or with peristaltic pumps.
  • the reaction temperature in the process according to the invention should be kept in the range from 20° to 80° C.
  • the alkali salts of the ⁇ -keto esters are directly obtained and may either be immediately further reacted or converted in the usual way by acidification (aqueous HCl--, aqueous H 2 SO 4 or acetic acid) into the free ⁇ -keto ester, the pH-value being adjusted to about 6.
  • acidification aqueous HCl--, aqueous H 2 SO 4 or acetic acid
  • the esters are purified preferably by distillation.
  • the solvent hexamethyl phosphoric acid triamide
  • the solvent is enriched in the organic phase which can be removed during the subsequent distillation stage.
  • the solvent does not have to be removed because it does not interfere with the subsequent reaction.
  • the procedure was as in test 9 above, except that 325 g of sodium hydride in 1800 cc of dimethyl carbonate and 200 cc of hexamethyl phosphoric acid triamide, and 500 g of pinacolone (92%) were used. The yield was 82%.
  • the pivaloyl acetic esters obtained according to the methods 1 - 10 above can be converted by reacting equimolar amounts of pivaloyl acetic esters and an substituted aniline such as e.g.
  • pivaloylacetic acid anilide coupler compounds e.g. of the formula ##STR3##
  • the pivaloylacetic acid anilide coupler compounds can be used in known manners for the preparation of photographic images in color photographic materials e.g. as following:
  • the photographic material is then developed after imagewise exposure behind a grey step wedge in a color developer containing N,N-diethyl-p-phenylene-diamine as color developer substance. After normal bleaching and fixing a yellow step wedge was obtained having an absorption maximum of 436 nm.
  • the compound of Example 2 can be converted with anilines to ⁇ -methyl-propionylacetanilides e.g. according to the method described above which can be used in photographic materials as so called white couplers.
  • the ⁇ -alkyl substituted ⁇ -keto-carbonic-acid-anilides react with oxidized color developer substances of the p-phenylene diamine type to form compounds which are not colored.
  • they are used in color photographic materials in photographic layers for diminishing the color fog produced by a certain amount of oxidation products of color developer substances which is present even in unexposed areas of the photographic image due to diffusion processes.
  • the aforementioned compound can be converted by reaction with anilines into valuable white couplers suitable for use in color photographic materials.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US05/557,268 1974-03-16 1975-03-11 Aliphatic β-keto esters Expired - Lifetime US4031130A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2412784A DE2412784C3 (de) 1974-03-16 1974-03-16 Verfahren zur Herstellung von aliphatischen ß -Ketoestern
DT2412784 1974-03-16

Publications (1)

Publication Number Publication Date
US4031130A true US4031130A (en) 1977-06-21

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US (1) US4031130A (enrdf_load_stackoverflow)
JP (1) JPS50126618A (enrdf_load_stackoverflow)
BE (1) BE826344A (enrdf_load_stackoverflow)
DE (1) DE2412784C3 (enrdf_load_stackoverflow)
FR (1) FR2264001B1 (enrdf_load_stackoverflow)
GB (1) GB1483948A (enrdf_load_stackoverflow)
IT (1) IT1032316B (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5965767A (en) * 1997-04-10 1999-10-12 Procter & Gamble Company Beta ketoester compositions and method of manufacture
US20060149094A1 (en) * 2004-12-30 2006-07-06 Zoeller Joseph R Process for generating pivaloylacetate esters via carbonylation of chloropinacolone

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
fieser et al., Reagents for Organic Synthesis, vol. 3, 149-150, (1970). *
House, Modern Synthetic Reaction, 744-754, (1972). *
Krapcho et al., Org. Synthesis, 47, 20 (1967). *
Normant, Angew. Chem. Int. 6, 1056, 1061, (1967). *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5965767A (en) * 1997-04-10 1999-10-12 Procter & Gamble Company Beta ketoester compositions and method of manufacture
US20060149094A1 (en) * 2004-12-30 2006-07-06 Zoeller Joseph R Process for generating pivaloylacetate esters via carbonylation of chloropinacolone

Also Published As

Publication number Publication date
DE2412784A1 (de) 1975-10-02
DE2412784B2 (de) 1979-09-13
FR2264001A1 (enrdf_load_stackoverflow) 1975-10-10
FR2264001B1 (enrdf_load_stackoverflow) 1978-12-29
DE2412784C3 (de) 1980-06-04
GB1483948A (en) 1977-08-24
IT1032316B (it) 1979-05-30
BE826344A (nl) 1975-09-08
JPS50126618A (enrdf_load_stackoverflow) 1975-10-04

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